Equilibrium Phase Compositions Research Articles

Phase equilibria studies of the CaO–SbOx system in air

AbstractThe phase equilibria information of the CaO–SbOx system in the range of 700–1580°C in air was obtained for the first time using quenching method and thermal analysis. The equilibrium phase compositions were determined using x‐ray diffraction and Scanning Electron Microscopy‐Energy Dispersion Spectrum. The invariant reaction temperatures were determined using thermogravimetry‐differential scanning calorimetry. A perovskite solid solution between Ca2Sb2O7 and CaO, designated as (Ca6Sb2O11)s.s, was observed. Within this solid solution, three polymorphic forms were identified: orthorhombic, tetragonal, and cubic. The transition temperatures between these polymorphic forms vary with compositional changes. Additionally, the crystal structure of cubic Ca6Sb2O11 was analyzed. CaSb2O6 was observed to decompose into Ca2Sb2O7, Sb4O6, and O2 above 1336 ± 5°C. The eutectic temperature of α‐Sb2O4 and CaSb2O6 was found to be 1220 ± 5°C.

Application of the methodology for modeling thesubsolidus phase composition within the framework of multicomponent oxide systems for controlling the slag regime of oxygen converter melting

A theoretical study of the subsolidus phase structure of multicomponent oxide systems CaO‒MgO‒Al2O3‒SiO2‒FeO‒Fe2O3 and CaO‒MgO‒Al2O3‒SiO2‒MnO‒TiO2 has been carried out. The separation of the CaO‒MgO‒Al2O3‒SiO2‒MnO‒TiO2 system into ensembles of mutually coexisting phases using the concept of optical basicity of oxide compounds is proposed. A technique for modeling the equilibrium phase composition within these systems based on their subsolidus phase structure is proposed. This technique is the basis for estimating the liquidus temperature and determining the areas of primary crystallization of phases based on the chemical composition of the slags of the converter process. The developed methodology and software based on it can be used to determine the limits of solubility of refractory phases in slag melts, and to numerically evaluate the slag corrosion of the lining of an oxygen converter.

Roles of Refractory Solutes on the Stability of Carbide and Boride Phases in Nickel Superalloys

Nickel-base superalloys contain high amounts of solutes like Cr, Mo, W, Nb, Ti, etc. These solutes promote the formation of different types of carbide and boride phases that may contain multiple elements. Researchers have mostly discussed the roles of primary elements responsible for the formation of a given carbide/boride phase, often ignoring the role of other solutes on its stability. In the present work, thermodynamic stability of carbide and boride phases in seven commercial superalloys, namely, Alloy 625, Alloy 690, Alloy 718, MAR M246, Rene 100, Udimet 710 and Nimonic 80A, has been studied using the CALPHAD based Thermo-Calc software. The aim of the study was to understand the role of different alloying elements on temperature stability and chemical compositions of equilibrium phases in superalloys. As the accuracy of CALPHAD based predictions depends upon the database used, a detailed examination of its inadequacies has also been carried out to ascertain the limitations of the predicted data. From the calculated equilibrium chemical compositions, major and minor constituents promoting the formation of carbides and borides have been identified. The individual effect of a given solute as well as the synergistic effect of two solutes on the relative thermodynamic stability of carbide/boride phases has been identified using property diagrams and isothermal sections of the temperature-composition diagrams. Most of the simulated results have been found to be consistent with the experimental data available in the literature. From a comparison of the experimental literature and the simulated data of the stable carbide and boride phases in the studied alloys, the interplay of different solutes has been deduced to define conditions under which these phases form, within the limitations of the database used. This study has helped in better understanding of general tendencies of solutes to form different carbide and boride phases in nickel-based superalloys.

Phase equilibria of CaO–Al2O3–CaO·TiO2 system at 1500 °C in hydrogen atmosphere

The phase diagram of CaO–Al2O3-TiOx system is of great importance in guiding the design of metallurgical slag systems for Al–Ti alloy steel, controlling Ti-bearing inclusions in molten steel, and regulating the mineral phase of vanadium-titanium magnetite. In the present work, the high temperature equilibration-quench technique was adopted, and the types and compositions of equilibrium phases were identified by Electron Probe Micro Analysis (EPMA) and X-ray diffraction (XRD). The isothermal section of CaO–Al2O3–CaO·TiO2 system at 1500 °C in H2 atmosphere was constructed for the first time. There are 7 three-phase fields, 10 two-phase fields, and a single liquid phase field. On this basis, according to the theoretical analysis of the crystal structure, the formation energy analysis based on first-principles calculations, and the related theories of defect chemistry, the formation mechanisms of CaTiO3 and Ca3Ti2O7 solid solution with were determined, respectively. Additionally, the experimental phase diagram was utilized to discuss the dissolution type and the equilibrium solubility of typical inclusions (Al2O3, Ti3O5, and CaO·TiO2) in Al–Ti alloy steel.

The phases formed in Sn/Co thin bilayer upon heating

The structure and phases formed in Sn/Co thin films are interesting both from the solid-state chemistry point of view and due to applications of such a metallic bilayer. The phases forming in thin films Sn/Co obtained by thermal vacuum evaporation on two different substrates SiO2 and MgO(100) at different annealing temperatures have been studied. Annealing above 110°С results in intermetallics formation in the films. The hcp-cobalt is grown in the films on SiO2 substrate, and the fcc-Co is observed on MgO(100) substrate. It is found that the stable α-Co3Sn2 intermetallic is formed at higher annealing temperature in film on MgO(100) substrate. We show that transformations related to mass transfer in the Sn/Co bilayers were up to 500°С and were finished upon reaching the thermodynamically equilibrium phase composition at this temperature.

Novel value-add recycling route of industry solid waste for acting as supporting skeleton of NaNO3 phase change materials (PCMs)

This study provided a value-added utilization route for industrial solid waste by converting them into porous ceramics to act as supporting skeleton for PCMs. Steel slag (SS), ferronickel-slag (FNS) and Fly ash (FA) was used as main raw material to prepared anorthite-cordierite (AC) porous ceramics. Five groups of formula with different phase content were designed by adjusting the amount of SS and FNS addition. FactSage 8.0 software was applied to calculate the equilibrium phase composition of AC at high temperature, which provided guidance for the actual high temperature synthesis process. The prepared AC porous ceramics were found to have good mechanical strength and high porosity. Good chemical compatibility between AC and NaNO3 was demonstrated and the infiltration ratio was varied from 42% to 45%. In addition to high thermal storage capacity, AC has been found to help reduce the supercooling of NaNO3 and helps to improve the thermal storage performance. After 100 thermal cycles of melting and freezing, NaNO3/AC C-PCMs could maintained high than 97% of latent heat. Thermal transfer properties of AC were significantly enhanced after molten NaNO3 infiltrated. The thermal conductivity of NaNO3/AC40 C-PCMs at 25 °C reached 1.60 W·(m·K)−1, which is more than three times that of pure NaNO3. The good thermal storage performance of NaNO3/AC C-PCMs makes it potential candidate in high-temperature thermal storage fields like industrial waste heat recovery and solar energy storage. In a word, the application potential of metallurgical slag in the field of energy saving was well demonstrated by this study.

The Direct Alloying of Steel through Silicothermic Self-Reduction of Chromite Ore Utilizing Si-Containing Solid Waste

Organosilicon materials generate copious amounts of Si-containing solid waste during production, leading to severe environmental pollution and substantial resource squandering. In pursuit of the resource utilization of Si-containing solid waste, this study conducted experimental research on the direct alloying of molten steel through the silicothermic self-reduction of chromite ore using Si-containing solid waste as a reducing agent. Additionally, thermodynamic analysis was performed, employing the thermodynamic calculation software FactSage 8.2 (Thermfact Ltd., Montreal, QC, Canada and GTT-Technologies, Aachen, Germany), to examine the equilibrium reactions of the silicothermic reduction of chromite ore and the variations in the thermodynamic equilibrium compositions of slag and metal phases. The results indicate a reduction sequence for the reducible components in chromite ore as Fe2O3 → Cr2O3. The introduction of CaO and Al2O3 into the silicothermic self-reduction compacts altered the forms of Fe and Cr oxides in equilibrium, significantly reducing the standard Gibbs free energy (ΔG0) of the silicothermic reduction reaction. The initial slag melting point decreased from 1700 °C without the addition of CaO and Al2O3 to 1500 °C with the addition of CaO and Al2O3. Correspondingly, the slag viscosity at 1600 °C decreased from 134.1 Pa·s without CaO and Al2O3 addition to 1.81 Pa·s with CaO and Al2O3 addition. The addition of CaO and Al2O3 accelerated the reduction of Cr oxide in chromite ore and enhanced the recovery of Cr, consistent with the thermodynamic calculation results. In the process of steelmaking through the direct alloying of chromite ore silicothermic self-reduction compacts, the final recovery rate of Cr increased from 86.4% without CaO and Al2O3 addition to 95.4% with CaO and Al2O3 addition.

Multiphase Equilibrium Relationships between Copper Matte and CaO-Al2O3-Bearing Iron Silicate Slags in Combined Smelting of WEEE and Copper Concentrates

Waste electrical and electronic equipment (WEEE) contains various valuable metals, making it a potential secondary resource for sustainable metal usage. Pyrometallurgical smelting is an efficient technique to recycle WEEE by extracting precious metals into copper matte and removing impurities into slags. The impact of WEEE impurities such as CaO and Al2O3 on the phase compositions of the smelting products attracts great attention for industrial metal recovery. This study clarified the impact of CaO and Al2O3 on the equilibrium phase compositions of copper matte and SiO2-saturated FeOx-SiO2-Al2O3-CaO slags. The high-temperature smelting experiments were taken at a controlled p(SO2) of 0.1 atm and 1300 °C, followed by quenching and electron probe microanalysis. The results showed that the copper and sulfur in the smelting system were highly deported into copper matte, and their distribution in matte was enhanced by increasing CaO and Al2O3 concentrations introduced by WEEE. The chemical copper dissolution in slags increased with increasing matte grade but decreased by adding CaO and Al2O3. The iron was preferentially concentrated in slags, and higher matte grades improved the iron distribution in slags. The current experimental results enrich fundamental thermodynamic data and help optimize WEEE smelting operations for efficient recovery of valuable metals.

Carbothermic Reduction of Copper Slag in the Presence of Borax

ABSTRACT The low temperature carbothermic reduction of copper slag with charcoal in the presence of borax followed by leaching with H2SO4 was investigated in this study. The copper slag sample was characterized using the XRD. Thermogravimetry was used to study the thermal degradation processes of copper slag. The standard Gibbs free energy at each reaction temperature was calculated using the HSC Chemistry® software. In the reduction experiments, the effects of charcoal and borax, as well as the reduction temperature and time, were investigated in order to identify the mechanism of enhanced reduction. The degree of metal dissolution was investigated in the leaching experiments in relation to leaching time and acid concentration. According to the results of the mineralogical analysis, the primary phases in the copper slag were fayalite, and magnetite. The HSC Chemistry results on equilibrium phase composition show that the carbothermic reduction of magnetite at various temperatures proceeded stepwise as Fe3O4 → FeO → Fe. Meanwhile, fayalite was first catalyzed at low temperature of 300°C before being reduced to metallic phase at 545oC. Thermochemical calculations, phase characterization and experimental results demonstrate that using borax in carbothermic reduction can accelerate phase transformation, lower the temperature of fayalite reduction, and improve the extraction of Co, Cu, and Fe at 850°C.

Integrated Experimental Phase Equilibria and Thermodynamic Modelling Research and Implementation in support of progress of process pyrometallurgy towards sustainability

Responding to the many sustainability challenges facing the metallurgical industry, we report progress that has been made on the development of predictive tools that can be applied to a wide range of technologies. The aim is to provide accurate, fundamentally-based thermodynamic tools that can be used by industry to improve process efficiencies, metal recoveries and productivities, and reduce energy requirements of pyrometallurgical systems. The program involves an integrated experimental and thermodynamic modelling research on phase equilibria in complex multi-component, multi-phase gas-slag-matte-speiss-metal-solids system with the Cu2O-PbO-ZnO-FeO-Fe2O3-CaO-Al2O3-MgO-SiO2-S major and As-Sn-Sb-Bi-Ag-Au-Ni-Co-Cr-Na minor elements. The experiments involve high temperature equilibration in controlled gas atmospheres, rapid quenching and direct measurement of equilibrium phase compositions with quantitative microanalytical techniques, including electron probe X-ray microanalysis and Laser Ablation ICP-MS. The thermodynamic modelling is undertaken using FactSage software package with advanced thermodynamic solution models. The continuing development of analytical and research methodologies has resulted in significant advances in predictive capability. Implementation of the results of fundamental studies involves ongoing collaboration of researchers and industry technologists, and the provision of advanced professional training. An overview of recent progress in research, implementation and applications in industrial practice will be presented in the paper.

Analysis of solid­phase reactions in the subsolidus of the CoO—Fe2O3—Al2O3 system

The article is devoted to studying the ternary system CoO—Fe2O3—Al2O3 structure with the determination of the thermodynamic equilibrium compositions of phases in its subsolidus. For theoretical studies in the CoO—Fe2O3—Al2O3 system, initial thermodynamic constants were calculated for CoAl2O4 and Fe2Al2O6. Subsequently, the entire possible array of exchange­type solid­phase reactions was simulated with the participation of stoichiometric compounds of the system. The possibility of destabilization of combinations of CoAl2O4 and CoFe2O4 phases in comparison with three­phase combinations was verified, namely, the article considered reactions not of the “2 = 2” type, but of the “2 = 3” type (two starting compounds and three compounds in the interaction products, or vice versa). It is noted that all possible variants of reactions of the “2 = 3” type in the CoO—Fe2O3—Al2O3 system can be modeled as linear combinations of exchange­type reactions with the participation of stoichiometric compounds of the system. The calculation of DG = f(T) values for them is reduced to a simple algebraic summation of the corresponding values of DG for the reactions that make up the combination of system phases. The calculations analysis of the change in Gibbs free energy with temperature in the range from 800 to 2000 K for the analyzed solid­phase reactions made it possible to carry out a complete triangulation of the CoO—Fe2O3—Al2O3 system with its division into elementary triangles. The geometrical and topological characteristics of the CoO—Fe2O3—Al2O3 system and its phases are determined. Information about phase relationships and thermodynamic stability of phase combinations can be useful in developing special­purpose refractory non­metallic materials. The use of compounds included in the elementary triangle CoO—CoFe2O4—CoAl2O4, which according to its geometric and topological characteristics has the maximum area, in the production of special materials with specified properties is proposed.

<em>In situ</em> study of mechanical properties and structural transformations during heating of WC–TaC–Co cemented carbides in a transmission electron microscope column

This study investigated the hardness of lamella with varying thickness, obtained from a massive, fine-grained cemented carbide comprising WC–6 %Co–0.2 %TaC, characterized by an average grain size of approximately 5 μm. The picoindentation method was employed for this analysis. Picoindentation was carried out using a Berkovich diamond indenter with a radius of curvature around 50 nm, and the experimental data were analyzed using the Oliver–Pharr model. The results revealed a significant correlation between hardness and lamella thickness. The hardness of the electron transparent section (thickness less than 100 nm) of the lamella measured 11.3±2.8 GPa, while the electron nontransparent section (thickness more than 200 nm) exhibited a hardness of 20.8±1.2 GPa. The lower hardness in electron transparent objects (thickness ~100 nm) is likely attributed to a combination of factors, including the potential bending of thin cobalt layers, the presence of edge effect, and closely spaced structural defect dislocations on the lamella surface. In situ TEM studies were conducted to examine structural transformations during the heating of WC–6 %Co–0.2 %TaC lamella, including in the presence of oxide phases (WOx ). Oxide phases on the lamella’s surface were generated by oxidizing the lamella at 200 °C in an air atmosphere. The results indicated that heating up to 500 °C did not bring about significant changes in the structure. However, at 600 °C, there was a notable thinning of cobalt layers due to intense surface diffusion of cobalt. Simultaneously, the formation of nanosized particles of the Co3W3C phase, ranging in size from 5 to 20 nm, was observed in the binder. These particles resulted from a shift in the equilibrium phase composition of the carbide, changing from a two phase region (WC + γ) to a three phase region (WC + γ + Co3W3C) as a consequence of the lamella’s oxidation.

Experimental investigation of the phase equilibria of CaO–Al2O3–TiO2 slag system at 1500 °C with p(O2)=10−3 atm

The phase diagram CaO–Al2O3–TiO2 slag system is of great importance for metallurgical processes, such as the utilization of Ti-bearing slag and optimization in Al–Ti alloy steel smelting process. In the present work, the high-temperature phase equilibrium experimental technique was adopted, and the type and composition of equilibrium phases were identified by Electron Probe Micro Analysis (EMPA) and X-ray diffraction (XRD). The iso-thermal section of CaO–Al2O3–TiO2 system at 1500 °C in Ar atmosphere was constructed for the first time. There are 10 three-phase fields (Liquid + CaO+3CaO·2TiO2, Liquid+3CaO·2TiO2+4CaO·3TiO2, Liquid + CaO·Al2O3+4CaO·3TiO2, CaO·TiO2+CaO·Al2O3+CaO·2Al2O3, CaO·2Al2O3+CaO·TiO2+CaO·6Al2O3, Liquid + Al2O3+Al2O3·TiO2, Liquid + CaO·TiO2+CaO·6Al2O3, Liquid + CaO·6Al2O3+Al2O3, Liquid + TiO2+Al2O3·TiO2, 4CaO·3TiO2+CaO·TiO2+CaO·Al2O3), 13 two-phase fields (Liquid + CaO, CaO+3CaO·2TiO2, Liquid + Al2O3, Liquid+3CaO·2TiO2, Liquid+4CaO·3TiO2, Liquid + TiO2, Liquid + CaO·TiO2, Liquid + Al2O3·TiO2, CaO·TiO2+CaO·2Al2O3, Liquid + CaO·6Al2O3, Liquid + CaO·Al2O3, 4CaO·3TiO2+CaO·TiO2, 4CaO·3TiO2+3CaO·2TiO2), 3 single-phase solid solution fields (4CaO·3TiO2(ss), 3CaO·2TiO2(ss), TiO2(ss)), and 2 independent single liquid phase fields. Besides, taking the Ti-bearing slag system as an example, the influence of oxygen potential on the activity of (TiOx) was discussed; furthermore, the reasonability of the valence state approximation of element Ti was farther evaluated.

Study of supersaturated solid solution decomposition during quenching of sheets from Al-Mg-Si aluminum alloy

This paper presents the results of a study of the stability of a supersaturated solid solution (SSS) of sheets made of thermally hardened aluminum alloy of the Al-Mg-Si system with a small addition of copper (Al-0.6Mg-1.0Si-0.2Cu) under various quenching modes. The samples were subjected to isothermal or continuous quenching with different quenching cooling rates, after which artificial aging was carried out at a temperature of 170°C. From the results of thermodynamic modeling of the equilibrium phase composition of the alloy, it was found that for the temperature range from 300 to 530°C, the presence of the β-phase (Mg2Si) is most likely. With the use of transmission electron microscopy and X-ray spectral microanalysis, it was found that during quenching, the decomposition of SSS leads to the precipitation of undesirable large particles of metastable β-type phases or equilibrium β-phase. The nucleation of the secretions is realized in the form of rod-shaped particles by a heterogeneous mechanism mainly on the surface of the α-phase dispersoids (Al15(Mn,Fe)3Si2), which thus significantly increase the quenching sensitivity of the alloy. The formation of these secretions at a low quenching rate causes, during subsequent aging, a decrease in the proportion and density of formation of strengthening particles of the β" phase, and also leads to an increase in their size and heterogeneity of distribution in the aluminum matrix, which reduces the potential of dispersion hardening during aging and corrosion resistance of the material.

Role of oxygen potential in dopant solubility in ferrite magnets: Enhanced Zn solubility and magnetization in La–Zn co-substituted magnetoplumbite-type strontium ferrite

To improve the performance of magnetoplumbite-type (M-type) AFe12O19 (A = Sr, Ba, Pb,…) hard ferrite magnets, such as the remanent magnetization and the coercivity, it is effective to dope transition metal elements at the Fe site. Substitution of nonmagnetic Zn, which preferentially occupies a minority-spin site in the ferrimagnets, is expected to increase magnetization. However, the solubility of Zn is limited to approximately 2–3% of Fe when synthesized in air. The solubility of divalent transition-metal substituents achieved by simultaneous substitution with trivalent cations on the A-site is often limited due to the auto reduction of Fe3+ to Fe2+. In this study, La–Zn co-substituted M-type strontium ferrites, Sr1−xLaxFe12−yZnyO19, were synthesized under different oxygen pressures of pO2 = 0.2, 1, and 10 atm, and the phase equilibrium and chemical composition were established by X-ray diffraction and wavelength dispersive X-ray spectroscopy. At pO2 = 10 atm, Sr-free La–Zn co-substituted ferrite, LaFe11.25Zn0.75O19, and single phases with actual compositions (x, y) = (0.42, 0.33) and (0.50, 0.45) were obtained for the first time. The single-phase samples exhibited a 5–9% higher saturation magnetization compared to non-doped SrFe12O19 at room temperature. Together with the coercivity enhancement by Co2+ substitution, oxygen potential control is a promising strategy to tune both coercivity and magnetization in future ferrite magnets.

The Effect of SiC on the Phase Composition and Structure of Mixed Slag

In order to investigate the influence of SiC on the composition and structure of mixed slag (blast-furnace slag: steel slag = 1:9), the chemical composition, equilibrium-phase composition, and microscopic morphological characteristics and elemental distribution in the microscopic region of the SiC-reagent-tempered slag samples were analyzed by X-ray diffractometer (XRD), FactSage7.1 thermodynamic analysis software, scanning electron microscope, and energy spectrum analyzer. It was found that the main physical phases of the tempered slag samples were magnesia–silica–calcite (Ca3Mg(SiO4)2, C3MS2), calcium–aluminum yellow feldspar (Ca2Al2SiO7, C2AS), C2S, and iron alloy. Theoretical calculations suggest that the experimental temperature should be higher than 1500 °C to facilitate the combination of P5+ with Fe and Mn in the liquid phase to form an alloy, reduce the P5+ content in the tempered slag, and create conditions for the self-powdering of the conditioned slag. The doping of the SiC reagent can increase the liquid phase line temperature and reduce the binary basicity in the liquid phase; the liquid phase line temperatures were 1150 °C, 1200 °C, and 1300 °C and the basicities in the liquid phase were 4.68, 4.13, and 3.10 for the doping amounts of 3%, 4%, and 5% of the SiC reagent, respectively. The mixed slag doped with 4% SiC reagent achieves self-powdering and reduction of ferroalloys during the air-cooling and cooling processes, realizing the purpose of “resource utilization” of blast-furnace slag and steel slag.

Experimental Study of the Combined Effects of Al2O3, CaO and MgO on Gas/Slag/Matte/Spinel Equilibria in the Cu–Fe–O–S–Si–Al–Ca–Mg System at 1473 K (1200ºC) and p(SO2) = 0.25 atm

The combined effects of Al2O3, CaO and MgO slagging components on phase equilibria and thermodynamics in the basic Cu–Fe–O–S–Si system have been evaluated at 1473 K (1200 ºC) and p(SO2) = 0.25 atm for a range of oxygen partial pressures and matte compositions. The experimental technique included high-temperature equilibration of the samples on a spinel substrate under controlled gas atmosphere (CO/CO2/SO2/Ar), followed by rapid quenching and subsequent measurement of the equilibrium phase compositions using Electron Probe X-ray Microanalysis (EPMA). The experimental data have been compared with the results of thermodynamic calculations undertaken using FactSage software and an internal thermodynamic database. Both the experimental results and the calculations results revealed that the presence of Al2O3, CaO and MgO reduced both the sulphur and copper concentrations in the slag phase for a given set of process conditions. The data have been used for further optimisation of the parameters of the thermodynamic database describing multicomponent metallurgical systems. The resulting thermodynamic database is capable of predicting, with high accuracy, the phase equilibria and the distribution of all elements between the phases in the Cu–Fe–O–S–Si–(Al, Ca, Mg) system.Graphical

Effect of carbon and tungsten content on the phase equilibria, microstructure, and mechanical properties of (Nb,W)C–Ni cermets

AbstractWith the assistance of thermodynamic simulation, the NbC–Ni based cermets with different W and C additions were designed and sintered in liquid state at 1390°C for 90 min in vacuum. By controlling the carbon and tungsten content, (Nb,W)C–Ni based cermets were prepared with varied phase constitution, microstructure, and mechanical properties. The microstructure, composition of phases, grain size, and equilibrium phases were investigated using scanning electron microscopy, electron probe microanalysis, EBSD, and X‐ray diffraction. The simulation reasonably predicted the experimentally observed phase constitutions. Depending on the additions, detailed analysis indicated that the cermets were composed of either a combination of cubic (Nb,W)C solid solution and Ni alloy binder or with an additional carbon‐deficient phase. Furthermore, mechanical analysis showed a strong dependence of its mechanical properties (Vickers hardness, indentation toughness, and flexural strength) on the phases and NbC grain size.

Separation of natural compounds using eutectic solvent-based biphasic systems and centrifugal partition chromatography

A study on the formation of ternary biphasic systems composed of heptane, 1-butanol or ethyl acetate and type III or type V deep eutectic solvents based on levulinic acid and choline chloride or thymol was carried. Binodal curves and densities and phase compositions of phases in equilibrium for seven systems are reported. The partition coefficients of six natural compounds, namely quercetin, apigenin, coumarin, β-ionone, retinol, and α-tocopherol, in these systems were measured. Results show that the influence of choline chloride on the partition coefficients is more significant in systems with 1-butanol or ethyl acetate than previously reported for ethanol, and that the separation of natural compounds is worst when using DES containing thymol instead of choline chloride. Based on these partition coefficients, one system composed of heptane, 1-butanol and the DES choline chloride:levulinic acid at molar ratio 1:3 was selected to be applied in centrifugal partition chromatography, and the results obtained confirmed that it allows a good separation of apigenin, coumarin, β-ionone and α-tocopherol.

Effect of CeO2 Content on Melting Performance and Microstructure of CaO-Al2O3-SiO2-MgO Refining Slag

CeO2 can be applied to refining slag to minimize the size of inclusions, speed up the deoxidization process, and adsorb Al2O3 inclusions. The impact through which CeO2 content affects slag’s melting efficiency is still uncertain. The thermal analyzer was used to measure the thermogravimetric analysis (TG) and differential scanning calorimetry (DSC) curves of the slag melting process. According to the study results, with the increase in CeO2 content, the melting temperature of slag decreased first and then increased. The slag’s melting point fell from 1364 °C to 1324 °C and then rose to 1503 °C. XRD and SEM were used to analyze the CaO-Al2O3-SiO2-MgO-CeO2 slag’s microstructure. The mineral-phase structure of CeO2-containing refining slag was primarily composed of Ca2SiO4 and 3CaO·Al2O3, MgO, SiO2, CaO·Al2O3, and Ca8Ce6Al6O26. The proportion of 3CaO·Al2O3, CaO·Al2O3, and Ca2SiO4 decreased as the rare-earth-oxide content increased, while the proportion of Ca8Ce6Al6O26 increased. FactSage was used to estimate the equilibrium-phase compositions of slags with various compositions, and a model for predicting melting points was carried out by a linear regression model. Results were obtained through the analysis of equilibrium-phase composition and crystal structure transformation. The main reasons for the melting point decrease were the change of degree of polymerization and the decrease in contents and complete melting temperature of high-melting-point Ca3Al2O6 and Ca2SiO4 compounds. The latter increase in melting point was due to the number of Ca8Ce6Al6O26 compounds and precipitation temperature increases and the complexity of the structural-network increases.